Process for the manufacture of high grade burning oils and antiknock motor fuels



Oct. 31, 1933. E. GOHR PROCESS FOR THE UFACTURE OF HIGH GRADE BURNING OILS AND ANTIKNOCK MOTOR FUELS Filed July 2, 1930 (swi /u M 5. WWW;

Patented Oct. 31, 1933 UNITED STATES PROCESS FOR THE MANUFACTURE OF HIGH GRADE BURNING OILS AND ANTI- KNOCK MOTOR FUELS Edwin J. Gohr, Baytown, Ten, assignor to Standard-I. G. Company Application July 2, 1930. Serial No. 465,365

4 Claims.

4 The present invention relates to an improved.

process for treating hydrocarbon oils with hydrogen under elevated temperature and pressure. The process applies specifically to a method for the manufacture of high grade burning oils in which oils not suitable for illuminating purposes obtained from the process are converted into motor fuels of excellent anti-detonating qualities. My invention will be fully understood from the following description and drawing which illustrates one form of my invention.

The drawing shows diagrammatically in sectional elevation an apparatus constructed according to my invention and indicates the flow of the various materials in the process.

Referring to the drawing, a hydrocarbon oil is fed from any suitable source by pump 1 through line 1a, where it may mix with a supply of gas rich in hydrogen from line 2, into the cooling coils of partial condenser 3. From 3 1311) material flows through line 4 to partial condenser 5. Both 3 and 5 are provided with bypass valves 3a and 5a in order to regulate the temperature within the partial condensers. Partial condenser 3 may also be provided with auxiliary cooling coil 3b, through which any suitable cooling fluid may be circulated in regulated amounts to aid in controlling the separation in the partial condenser. After leaving the coils of partial condenser 5, the material passes through line 6 to heating coil 7, mounted in suitable furnace 8. Hydrogen may be added in place of that, or in addition to that from line 2, at the coil inlet by means of line 9. Coil 7 discharges into reaction drum 10 which is constructed to withstand temperatures of 850 F., or higher, and pressure of several hundred atmospheres, as well as the corrosive. effect of the 40 reactants. Drum 10, is provided with suitable insulation 11 and is packed with a suitable catalytic material 12, which may be packed into the drum in lump form or may be supported upon trays or upon other surfaces arranged in the drum. Additional hydrogen may be added to the reaction drum 10 by means of line 13.

The mixture of oil and hydrogen flow up through the catalytic mass 12, where reaction takes place, yielding large percentages of high grade burning oil. The gas and vapor pass from the drum through line 14 to partial condenser 5 whichis maintained at a temperature such as to condense out fractions too heavy for burning oils. The condensate from 5 is removed by line 15 and may be recycled to coil 7 and reaction drum 10 by pump 16 and line 1'7 for conversion to burning oil. If desired, all or part of the condensate from 5 may be sent through line 18 to the second stage of theprocess for conversion to anti-detonating gasoline, or the condensate may be withdrawn by line 19 for any suitable purpose, such as charging to cracking coils. The uncondensed vapor from 5 flows by line 20 to partial condenser 3, where the burning oil fraction may be condensed and withdrawn by line 21, while gas and vapor pass out by line 22. It will be understood that other separation means such as a packed or bubble plate column, may be employed in place of the partial condensers.

The vapor, which may consist of gasoline or naphtha, and the gas in line 22 may beconducted by lines 23 and 25 to heat exchanger 26 and the second stage of the process where these low boiling oils are treated to produce anti- 76 detonating motor fuel. If there is too great an excess of gas with the vapor, all or part of the material in line 22 may be passed through condenser 27 into separator 28 from which this condensed oil may be passed through lines 29 and 25 so to exchanger 26, while gas is removed by line 30. Where the second stage of the process is operated at a pressure equal to, or in excess of that in the first reactor, the pump 24 may be employed to raise the pressure on the liquid in drum 85 28. If desired, part of the condensate from drum 28 may be withdrawn from the process through connection 32, or in certain cases, oil from an outside source may be supplied by means of 32. After leaving heat exchanger 26, the oil flows through line 33 to heating coil 34, mounted in furnace 35. Coil 34 discharges into reaction drum 36, which is designed to withstand temperatures in excess of 950 F. and pressures of several hundred atmospheres.

Hydrogen may be added to the oil in this sec- 0nd stage of treatment in any desirable way. For example, hydrogen from the first stage may be employed by means of line 23, as previously explained, or hydrogen may be obtained inde- 10o pendently for the second stage by line 31, or at the coil inlet by line 3'7, or in the reaction drum 36 by line.38, or all, or combinations of these methods may be utilized.

Reaction drum 36 is insulated and is packed with a suitable catalyst 39 which may or may not be of the samecomposition as thatin reaction drum 10. After passing through catalyst 39, where the oil is converted to motor fuel of excellent anti-detonating characteristics, the oil vapor and gas flow out through line 40 to heat exchanger 26, and separator 41, where the vapor condensed in the exchanger is collected. If gas-is being removed from separator 28 by line 30, a portion or all of this gas may be added to the hot material in line 40 by means of line 42. Condensate, consisting of motor fuel, may be drawn from separator 41 by line 43, while the gas is taken off through pipe 44. Gas from separator 30 may be added to 44 at this point by use of line 45. From 44 the gas passes to a suitable purification system 46 for removing hydrogen sulfide and gaseous hydrocarbons. The purification may consist of a scrubbing treatment with heavy oils or with soda ash solution. The purified gas flows to booster compressor 47 which discharges into line 31 and manifold 48 for repassage through the process. Fresh or makeup hydrogen may be added to the inlet of compressor 47 by line 49.

In the operation of my process the feed stock may consist of hydrocarbon oil distillates such as heavy naphtha, gas oil cuts, or oils boiling in the kerosene range. My process is especially applicable to oils of the above type, which contain a substantial proportion of non-paraflinio hydrocarbons or other materials which make them unsatisfactory for illuminating purposes.

When these feed stocks are hydrogenated to produce high grade burning oils, fractions of a boiling point too low for this purpose are formed the process. These fractions may consist of highly saturated gasoline, naphtha and the like,

and may amount to 10 to 45 percent of the feed oil, depending on the severity of the hydrogen treatment. A more intensive treatment produces a larger percentage of lower boiling oils as will be understood. In my improved process I propose to convert these oils which are too light for illuminants, and which knock badly when used as motor fuel, owing to their highly saturated condition, into high grade anti-detonating gasoline by passing them through an additional reaction stage in the presence of hydrogen. The first stage, in which high grade illuminating oils are formed, will be referred to as the primary stage, while that in which the low boiling oils are given additional treatment to convert them to anti-knock motor fuel, will be known as the secondary hydrogenation stage.

In carrying out my process the feed oil is heated, preferably with hydrogen, to a temperature not exceeding about 840 F. by rapid passage through a heated coil. The heated mixture then passes under high pressure to the reaction drum of the primary stage. The drum is packed with a suitable catalyst which may comprise the oxidesand/or sulfides of elements of the sixth group of the periodic table, their mixtures with each other or with other compounds such as zinc oxide, magnesia, lime or alumina, these catalysts being characterized by resistance to sulfur. Such catalysts may be generally classified as sulfactive.

V The primary reaction drum is preferably maintained at a temperature between about 700 and 810 F., the heat supplied to the reactants in the coil and the heat of the reaction being sufflcient .to maintain the temperature of the reaction drum.

reaction drum. The oil feed rate to the primary stage is preferably held between about 0.3 and 1.5 volumes of oil per volume of reaction drum per hour.

The hydrogen and feed oil in flowing through the catalytic mass react to form illuminating oils of high quality as regards sulfur, color, candle power, and general burning characteristics. The product from the primary reactor also contains lower boiling distillate, as mentioned before, as well as a small amount of material too heavy for illuminants. The product is therefore separated into these three fractions.

This separation may be carried out by any suitable means, such as partial condensers, bubble plate towers, and the like. The illuminating oil fractions are preferably withdrawn from this separation means and sent to storage. In some cases it is desirable to submit this oil to a slight caustic wash previous to storage. No acid treatment is required, however.

The heavier unconverted oils may be returned to the primary reaction drum for conversion to burning oil or they may be sent to the secondary reaction drum along with the low boiling oils for conversion into anti-knock gasoline. In some cases it is desirable to withdraw these heavier fractions for various purposes such as charging to cracking coils.

The fractions of a boiling point too low for burning oil are passed to a heating coil where they are heated to a temperature between about 850 and 950 F. at a high rate sufficient to prevent carbon deposition. The coil discharges into the secondary reactor which is packed with a suitable catalyst, which may or may not be of the same composition as that in the primary reactor, but which contains, in general, constituents which were stated as suitable for the primary stage.

Hydrogen may pass through the coil with the 115 oil, or it may be introduced separately into the secondary reactor in a heated or unheated condition. The hydrogen may consist of that employed in the primary stage, or fresh hydrogen or both, may be used. Contrary to the primary stage, 120 where 'a large excess of hydrogen is employed, only sufiicient hydrogen is used in the secondary reactor to prevent formation of coke or asphaltic materials. If too great an excess is used, the knock-suppressing qualities of the product are lessened. It is preferable, therefore, to employ hydrogen in an amount equivalent to about 1000 to 4000 cubic feet per barrel of oil fed to the secondary reactor. The pressure may be substantially the same as that in the primary, or may be higher or lower, but is ordinarily in excess of 20 atmospheres and preferably about 100, to 200 atmospheres.

The secondary reactor is maintained at a temperature above about 900 F. and preferably in the range between about 920 and 980 F. Heat of reaction in the reaction drum and heat added to the reactants in the coil serves to maintain the temperature in the reactor, which is insulated. The feed rate to the secondary reactor is dependent on the degree of improvement desired in the product, and is lower for greater improvement, as will be understood. In general, the feed rate may be taken between about 1.5 and 4.5 volumes of oil per volume of reactor per hour.

This additional stage of treatment for the low boiling oils serves to convert them to motor fuel or motor fuel blending agents of high anti-detonating characteristics. The gasoline so obtained is also superior as regards low sulfur, excellent 150 color, and small content of gum forming materials.

As an example of my method the-following kerosene distillate was charged to my process:

Gravity A. P. I 39.6 Int. boiling pt. F 220 Percent 374 F 9.5 Percent 400 F 15.5 Percent 460 F 41.0 Final boiling pt. "F 592 Percent sulfur 0.260 Saybolt thermo vis. 60 F 485 see.

This feed stock was passed with an excess of hydrogen through a reactor packed with a lump catalyst composed of the oxides of chromium, molybdenum and tungsten. The feed rate is expressed in volumes of oil per volume of reactor 4 space per hour. The amount of gas passed through the reactor with the oil is expressed in cubic feet per barrel of feed oil. The conditions of operation were as follows:

Reactor temperature F 820 Feed ratevol./vol./hr 0.66 Gas ratecu.ft./bbl 6000 Reactor pressu1 e-atm 200 The product obtained as a result of the above treatment contained about 75 percent of high grade kerosene of the following characteristics:

Gravity A. P. I 45.1 Saybolt thermo vis. 60 F 400 sec; Abel flash point F 122 Sulfur+percent 0.013

The product also contained about 20 percent of gasoline of detonating characteristics equivalent to those of gasoline of an ordinary sweet crude. This gasoline was charged to the second stage of my process where a reactor filled with a lump catalyst consisting of the oxides of chromium' 40 percent benzol. In addition to this the gasoline was similar to the following inspection:

Gravity A. P. I .r 54.0 Percent sulfur 0.005 Dissolved gum--mg./ 100 cc 12.5

My invention is not to be limited by any theory of the mechanism of the reactions nor to any specific example which may have been given for purpose of illustration, but only by the following claims in which I wish to claim all novelty inherent in my invention.

I claim:

1. An improved process for obtaining valuable products from hydrocarbon oils, comprising passing the oil through a reaction zone at a temperature between approximately 700-830 F. while under hydrogen pressure of at least 20 atmospheres, the oil rate being below about 1.5 volumes per hour per volume of reaction space containing a sulfactive catalyst and the hydrogen volume being at least 5,000 cu. ft. per barrel of oil, whereby a part of the oil is converted into an oil suitable for illuminating purposes and part into an oil unsuitable for such use, separating the parts and passing the one unsuitable for such use through a second reaction zone containing a second sulfactive catalyst under hydrogen pressure in excess of 20 atmospheres. at temperature above about 900 F., the oil rate being in excess of 1.5 volumes per hour per volume of reaction space and the volume of hydrogen being approximately 1,000-4,000 cu. ft. per barrel of oil, where by a low boiling product of valuable anti-detona tion properties is produced.

- 2. Process according to claim 1 in which the oil rate through the second reaction zone is between the limits of 1.5 and 4.5 volumes per hour per volume of reaction space and the temperature is between the approximate limits of 900-980 F.

3. Process according to claim 1 in which the oil rate through the first reaction zone is within the limits of .3 to 1.5 volumes of oil per hour per volume of reaction space.

4. Process according to claim 1 in which the hydrogen pressure in the first zone is between the limits of200 to 1,000 atmospheres and the hydrogen pressure in the second zone is between the limits of 20 to 200 atmospheres.

EDWIN J. GOHR. 

